CN115380248A - Photosensitive resin composition, cured product, color filter, member for display device, and display device - Google Patents

Photosensitive resin composition, cured product, color filter, member for display device, and display device Download PDF

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Publication number
CN115380248A
CN115380248A CN202180013052.0A CN202180013052A CN115380248A CN 115380248 A CN115380248 A CN 115380248A CN 202180013052 A CN202180013052 A CN 202180013052A CN 115380248 A CN115380248 A CN 115380248A
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Prior art keywords
photosensitive resin
group
resin composition
copolymer
pigment
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中川泰伸
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Daicel Corp
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Daicel Corp
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Priority claimed from JP2020039964A external-priority patent/JP7483416B2/en
Priority claimed from JP2020039965A external-priority patent/JP7483417B2/en
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Publication of CN115380248A publication Critical patent/CN115380248A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

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Abstract

The invention provides a photosensitive resin composition which has excellent storage stability, excellent curing reactivity and excellent solvent resistance of a cured product. A photosensitive resin composition comprising: an alkali-soluble resin which is a copolymer comprising a constituent unit (A) derived from an unsaturated carboxylic acid or an acid anhydride thereof and a constituent unit (B) derived from a compound represented by the following formula (1) (wherein R is R), a photopolymerizable compound, a photopolymerization initiator, and a solvent 1 And R 2 Each represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond, a divalent hydrocarbon group, or the like. Y represents a methylene group, an ethylene group or the like optionally having an alkyl group having 1 to 3 carbon atoms as a substituent. n represents an integer of 0 to 7), wherein the alkali-soluble resin is a copolymer having an exothermic peak top temperature of 180 to 220 ℃ which occurs when the temperature is raised at a rate of 5 ℃/min using a differential scanning calorimeter.

Description

Photosensitive resin composition, cured product, color filter, member for display device, and display device
Technical Field
The present disclosure relates to a photosensitive resin composition, a cured product, a color filter, a member for a display device, and a display device. The present application claims priority from Japanese patent application No. 2020-039964 and Japanese patent application No. 2020-039965, which are applied to Japanese patent application No. 3/9/2020, and the contents thereof are incorporated herein by reference.
Background
As photosensitive resin compositions used for producing insulating films, color filters, color filter protective films, and microlenses, resin compositions containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and resin compositions further containing a colorant (pigment, dye) are known.
Patent documents 1 and 4 disclose copolymers containing methacrylic acid and glycidyl methacrylate as constituent monomers as the alkali-soluble resins. Patent documents 2 and 5 disclose alkali-soluble resins as the alkali-soluble resinComprising methacrylic acid and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester as a copolymer of the constituent monomers. Patent document 3 discloses, as the alkali-soluble resin, a copolymer containing methacrylic acid and benzyl methacrylate as constituent monomers.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. H11-133600
Patent document 2: japanese patent laid-open No. 2006-171160
Patent document 3: japanese laid-open patent publication No. 9-134004
Patent document 4: japanese patent laid-open publication No. 2011-237728
Patent document 5: japanese patent laid-open No. 2007-333847
Disclosure of Invention
Problems to be solved by the invention
However, the photosensitive resin compositions disclosed in patent documents 1 and 4 have a disadvantage of low stability such as thickening over time. Furthermore, the solvent resistance of the cured product is also insufficient. The photosensitive resin compositions disclosed in patent documents 2 and 5 have excellent storage stability, but have poor reactivity with carboxylic acids and require a curing temperature of 230 ℃ or higher. The photosensitive resin composition disclosed in patent document 3 has a disadvantage that the solvent resistance of the cured product is low.
Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent storage stability, excellent curing reactivity, and excellent solvent resistance of a cured product.
Another object of the disclosed invention is to provide a cured product of the photosensitive resin composition having the above characteristics, a color filter as the cured product, and a member for a display device or a display device provided with the color filter.
Technical scheme
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: the photosensitive resin composition using a copolymer containing a specific constituent unit and having an exothermic peak top temperature of 180 to 220 ℃ as an alkali-soluble resin is excellent in storage stability, can be cured at a relatively low temperature, and is excellent in solvent resistance of a cured product. The invention of the present disclosure has been completed based on these findings.
That is, the present disclosure provides a photosensitive resin composition comprising:
an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
the alkali-soluble resin is a copolymer comprising a constituent unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a constituent unit (B) derived from a compound represented by the following formula (1),
[ chemical formula 1]
Figure BDA0003783774750000021
(in the formula, R 1 And R 2 Each of which may be the same or different, represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond or a divalent hydrocarbon group optionally containing heteroatoms. Y represents a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer of 0 to 7),
wherein the alkali-soluble resin is a copolymer having a peak temperature of an exothermic peak of 180 to 220 ℃ at a temperature rise of 5 ℃ per minute using a differential scanning calorimeter.
The copolymer may further include a constituent unit (C) derived from at least one compound selected from the group consisting of the following (C1) to (C4).
(c1) Styrene optionally substituted with alkyl;
(c2) An N-substituted maleimide;
(c3) An N-vinyl compound; and
(c4) An unsaturated carboxylic acid derivative represented by the following formula (2),
[ chemical formula 2]
Figure BDA0003783774750000031
(wherein R is 11 Represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R is 12 Represents a hydrocarbon group optionally containing heteroatoms. Z represents a heteroatom).
The proportion of the constituent unit (a) may be 2 to 60 wt%, the proportion of the constituent unit (B) may be 40 to 98 wt%, and the proportion of the constituent unit (C) may be 0 to 85 wt%, based on the total constituent units of the copolymer.
The photosensitive resin composition of the present disclosure may further include a color material.
The color material may be a pigment and/or a dye.
Further, the present disclosure provides a cured product of the photosensitive resin composition.
Further, the present disclosure provides a color filter which is a cured product of the photosensitive resin composition.
Further, the present disclosure provides a member for a display device or a display device including the color filter.
Effects of the invention
The invention disclosed herein provides a photosensitive resin composition which has excellent storage stability, excellent curing reactivity, and excellent solvent resistance of a cured product. Also provided are a cured product of the photosensitive resin composition having the above properties, a color filter as the cured product, and a member for a display device or a display device provided with the color filter.
Detailed Description
The photosensitive resin composition of the present disclosure is mainly used as a material for forming an insulating film, a color filter protective film, a microlens, a colored pattern, or the like, a transparent film, and comprises an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The photosensitive resin composition of the present disclosure may further contain a color material.
< alkali-soluble resin >
In the present disclosure, as the alkali-soluble resin, the following copolymers are used: the copolymer comprises a constituent unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a constituent unit (B) derived from a compound represented by the formula (1), and the copolymer has an exothermic peak top temperature of 180 to 220 ℃ when heated at a rate of 5 ℃/min using a differential scanning calorimeter. The copolymer may further contain a constituent unit (C) derived from at least one compound selected from the group consisting of the above (C1) to (C4). Further, the constituent unit (D) described later may be included as a constituent unit other than the constituent units (a) to (C).
[ constituent Unit (A) ]
The constituent unit (a) may be incorporated into the copolymer by subjecting the unsaturated carboxylic acid or its anhydride (a) to copolymerization.
The unsaturated carboxylic acid or its anhydride (a) is not particularly limited, and examples thereof include: α, β -unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.; α, β -unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, etc.; anhydrides of α, β -unsaturated monocarboxylic acids such as methacrylic anhydride; anhydrides of α, β -unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride. Among these, acrylic acid and methacrylic acid are particularly preferable from the viewpoint of copolymerizability and developability. The unsaturated carboxylic acid or anhydride (a) thereof may be used alone or in combination of two or more.
The proportion (content) of the constituent unit (a) relative to the total constituent units of the copolymer is not particularly limited, and is, for example, preferably 2 to 60% by weight, more preferably 3 to 40% by weight, and still more preferably 5to 20% by weight. When the proportion of the constituent unit (a) is within the above range, the cured product tends to have excellent solvent resistance and developability. In the present disclosure, the proportion of the constituent unit in the copolymer is based on the weight of the compound (monomer) used for copolymerization. For example, the proportion of the constituent unit (a) in the copolymer means the proportion of the amount of the unsaturated carboxylic acid or its anhydride (a) used relative to the total amount (100% by weight) of the compounds used for copolymerization.
[ constituent Unit (B) ]
The constituent unit (B) can be incorporated into the copolymer by copolymerizing a compound represented by the following formula (1).
[ chemical formula 3]
Figure BDA0003783774750000051
In the formula (1), R 1 And R 2 Each represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, which may be the same or different. X represents a single bond or a divalent hydrocarbon group optionally containing heteroatoms. Y represents a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer of 0 to 7.
As R 1 And R 2 The alkyl group having 1 to 7 carbon atoms in (1) includes, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl and the like. When n is 2 or more, n R 2 May be the same or different. From the viewpoint of copolymerizability and reactivity, R 1 And R 2 Preferably a hydrogen atom, a methyl group or an ethyl group.
In the divalent hydrocarbon group of X optionally containing a heteroatom, the heteroatom may be bonded to the terminal of the hydrocarbon group or may be sandwiched between carbon atoms constituting the hydrocarbon group. The hetero atom is not particularly limited, and examples thereof include: nitrogen atom, oxygen atom, sulfur atom.
As the divalent hydrocarbon group optionally containing the hetero atom, for example, there may be mentioned: an alkylene group such as a methylene group, an ethylene group, a propylene group, or a trimethylene group (preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms); a thioalkylene group such as a thiomethylene group, a thioethylene group, or a thiopropylene group (preferably a thioalkylene group having 1 to 12 carbon atoms, more preferably a thioalkylene group having 1 to 6 carbon atoms); an aminoalkylene group such as an aminomethylene group, an aminoethylene group, or an aminopropylene group (preferably an aminoalkylene group having 1 to 12 carbon atoms, more preferably an aminoalkylene group having 1 to 6 carbon atoms). Among them, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable, from the viewpoint of storage stability.
The methylene group or the ethylene group which may be substituted by an alkyl group having 1 to 3 carbon atoms as the substituent for Y is not particularly limited, and a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
Examples of the sulfur atom optionally bonded to an oxygen atom of Y include a sulfur atom, a sulfonyl group and the like.
Examples of the compound represented by the formula (1) include a compound represented by the following formula (1 a).
[ chemical formula 4]
Figure BDA0003783774750000061
R in the formula (1 a) 1 、R 2 X, Y and n have the same meanings as defined in the formula (1).
Specific examples of the compound represented by the formula (1) include the following compounds.
[ chemical formula 5]
Figure BDA0003783774750000071
The proportion (content) of the constituent unit (B) relative to the total constituent units of the copolymer is not particularly limited, but is preferably 40 to 98% by weight, more preferably 60 to 95% by weight, and still more preferably 75 to 90% by weight. When the proportion of the constituent unit (B) is within the above range, the cured product tends to have excellent solvent resistance and developability.
[ constituent Unit (C) ]
The constituent unit (C) is a constituent unit derived from at least one compound selected from the group consisting of the following (C1) to (C4): optionally alkyl-substituted styrene (c 1), N-substituted maleimide (c 2), an N-vinyl compound (c 3), and an unsaturated carboxylic acid derivative (c 4) represented by the formula (2). The constituent unit (C) has the following functions: a function of imparting hardness to a cured product (cured film), a function of smoothing a copolymerization reaction, a function of improving solubility in a solvent, a function of improving adhesion to a base material, and the like.
The constituent unit (C) may be incorporated in the copolymer by copolymerizing at least one compound selected from the group consisting of the above-mentioned (C1) to (C4).
(styrene (c 1))
The alkyl group in the styrene (c 1) optionally substituted with an alkyl group is not particularly limited, and examples thereof include: an alkyl group having 1 to 7 carbon atoms such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group and the like. Among these, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group is preferable, and a methyl group is more preferable. The alkyl group may be bonded to any of a vinyl group and a benzene ring of styrene.
As representative examples of styrene (c 1) optionally substituted by alkyl groups, mention may be made of: styrene, alpha-methylstyrene, vinyltoluenes (o-vinyltoluene, m-vinyltoluene, p-vinyltoluene), and the like. The styrene (c 1) optionally substituted with an alkyl group may be used alone or in combination of two or more.
(N-substituted maleimide (c 2))
Examples of the N-substituted maleimide (c 2) include compounds represented by the following formula (3).
[ chemical formula 6]
Figure BDA0003783774750000091
In the formula (3), R 21 Represents an organic group.
Examples of the organic group include a hydrocarbon group and a heterocyclic group. Examples of the hydrocarbon group include: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and hexyl (e.g. C) 1-6 Alkyl, etc.); cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl, and the like; aryl groups such as phenyl; aralkyl groups such as benzyl; and groups formed by bonding two or more of them together. Examples of the heterocyclic group include groups containing a nitrogen atomA five-to ten-membered heterocycloalkyl group and a heteroaryl group containing at least one heteroatom selected from the group consisting of oxygen atom and sulfur atom.
The N-substituted maleimide (c 2) is not particularly limited, and examples thereof include: n-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide and N-propylmaleimide; n-cycloalkylmaleimides such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide, N-adamantylmaleimide, and N-norbornylmaleimide; n-arylmaleimides such as N-phenylmaleimide; n-aralkyl maleimides such as N-benzyl maleimide. The N-substituted maleimide (c 2) may be used alone or in combination of two or more. (N-vinyl Compound (c 3))
The N-vinyl compound (c 3) is not particularly limited, and examples thereof include: n-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylpiperidone, N-vinylcaprolactam, and the like. The N-vinyl compound (c 3) may be used alone or in combination of two or more. (unsaturated Carboxylic acid derivative (c 4))
The unsaturated carboxylic acid derivative (c 4) can be represented by the following formula (2).
[ chemical formula 7]
Figure BDA0003783774750000101
In the formula (2), R 11 Represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R is 12 Represents a hydrocarbon group optionally containing heteroatoms. Z represents a heteroatom.
As R 11 The alkyl group having 1 to 7 carbon atoms in (b) includes, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl and the like. As R 11 Particularly, a hydrogen atom or a methyl group is preferable.
As R 12 The hydrocarbon group optionally containing a hetero atom in (1) may, for example, be exemplified by: alkyl, heteroalkylAlkenyl, cycloalkyl, heterocycloalkyl, aryl, and a group formed by connecting two or more of these. Examples of the hetero atom include: nitrogen atom, oxygen atom, sulfur atom.
Examples of the alkyl group include: an alkyl group having 1 to 23 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an isodecyl group, a lauryl group, and a stearyl group.
Examples of the heteroalkyl group include: - (R) 13 -O)m-R 14 Group (in the formula, R 13 Represents an alkylene group having 1 to 12 carbon atoms. R 14 Represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. m represents an integer of 1 or more), -R 15 -NR 16 R 17 Group (in the formula, R 15 Represents an alkylene group having 1 to 12 carbon atoms. R is 16 And R 17 Each of which may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
Examples of the alkenyl group include: an alkenyl group having 2 to 23 carbon atoms such as an allyl group, a 3-butenyl group, a 5-hexenyl group and the like.
Examples of the cycloalkyl group include: a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a norbornyl group and the like.
Examples of the heterocycloalkyl group include: examples of the group include groups having a cyclic ether structure (for example, groups containing a cyclic ether having three or more ring members), such as an oxetane (oxolane) ring, an oxolane (oxolane) ring, an oxirane ring, and an oxepane (oxolane) ring.
Examples of the aryl group include: aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl.
The unsaturated carboxylic acid derivative (c 4) represented by the formula (2) is not particularly limited, and examples thereof include: alkyl group-containing (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate) An acrylate; (meth) acrylates having an alkylamino group such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, and N, N-diisopropylaminoethyl (meth) acrylate; (meth) acrylates having a heteroalkyl group such as a hydroxyl group-containing (meth) acrylate (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, isooctyloxy diethylene glycol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and polyalkylene glycol (meth) acrylate such as methoxy polyethylene glycol (meth) acrylate; (meth) acrylates having an alkenyl group such as allyl (meth) acrylate; cyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5,2,1,0 2,6 ](meth) acrylates having a monocyclic or polycyclic cycloalkyl group such as decane-8-ol (meth) acrylate; glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyl oxyphenyl (meth) acrylate and other (meth) acrylates having an epoxy group (oxirane group), oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl-3-oxetanyl) ethyl (meth) acrylate, 2- [ (3-methyl-3-oxetanyl) methyl (meth) acrylate]Ethyl ester, 2- [ (3-ethyl-3-oxetanyl) methyloxy (meth) acrylate]Ethyl ester, 3- [ (3-methyl-3-oxetanyl) methyloxy (meth) acrylate]Propyl ester, 3- [ (3-ethyl-3-oxetanyl) methyloxy (meth) acrylate](meth) acrylate having oxetanyl group such as propyl ester, and tetrahydro (meth) acrylate(meth) acrylates having an oxetanyl group such as furfuryl ester; (meth) acrylates having a heterocycloalkyl group (e.g., a group containing a cyclic ether having three or more members), such as (meth) acrylates containing an alicyclic epoxy group (e.g., a group containing a cyclic ether having three or more members), such as 3, 4-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 2- (3, 4-epoxycyclohexyl) ethyl (meth) acrylate, 2- (3, 4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate, 3- (3, 4-epoxycyclohexylmethyloxy) propyl (meth) acrylate, and the like; aryl group-containing (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; alkoxysilyl group-containing (meth) acrylates such as 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 8- (meth) acryloyloxyoctyltrimethoxysilane. The unsaturated carboxylic acid derivative (c 4) represented by the formula (2) may be used alone or in combination of two or more.
The proportion (content) of the constituent unit (C) relative to the total constituent units of the copolymer is not particularly limited, but is preferably 0 to 85% by weight, more preferably 1 to 60% by weight, and still more preferably 2 to 40% by weight. When the proportion of the constituent unit (C) is within the above range, the cured product tends to have excellent solvent resistance.
[ constituent Unit (D) ]
The copolymer in the present disclosure may contain a constituent unit (D) other than the constituent units (a) to (C). Examples of the constituent unit (D) include constituent units derived from (meth) acrylamide and (meth) acrylonitrile.
In the case where the copolymer of the present disclosure includes the constituent unit (a) and the constituent unit (B) and does not include the constituent unit (C), the total amount of the constituent unit (a) and the constituent unit (B) is preferably 90% by weight or more, more preferably 95% by weight or more, further preferably 99% by weight or more, and may be substantially 100% by weight, based on the total constituent units. In the case where the copolymer of the present disclosure includes the constituent unit (a), the constituent unit (B), and the constituent unit (C), the total amount of the constituent units (a) to (C) is preferably 90% by weight or more, more preferably 95% by weight or more, further preferably 99% by weight or more, and may be substantially 100% by weight, based on the total constituent units.
The weight average molecular weight (Mw) of the copolymer is not particularly limited, and is, for example, preferably 1000 to 1000000, more preferably 3000 to 300000, and still more preferably 5000 to 100000. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: mw/Mn) of the copolymer is not particularly limited, but is, for example, preferably 5.0 or less, more preferably 1.0 to 4.5, and still more preferably 1.0 to 4.0. In the present disclosure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by GPC using polystyrene as a standard substance, for example, and are preferably measured by the method used in examples.
The polymer in the present disclosure has an exothermic peak top temperature of 180 to 220 ℃ occurring when heated at a rate of 5 ℃/min using a differential scanning calorimeter. In the present disclosure, the exothermic peak top temperature is preferably a temperature measured by a method used in examples described later, for example.
The copolymer in the present disclosure functions as a binder resin of the photosensitive resin composition of the present disclosure.
< method for producing copolymer >
The copolymer in the present disclosure can be produced by: copolymerization is performed on an unsaturated carboxylic acid or an acid anhydride thereof, (a) a compound (b) having a polycyclic aliphatic group having an epoxy group on the ring and a group having an unsaturated bond, at least one compound selected from the group consisting of the above (c 1) to (c 4) as required, and a compound corresponding to the above constituent unit (D). Hereinafter, the compound capable of being incorporated in the copolymer of the unsaturated carboxylic acid or its anhydride (a) and the like may be collectively referred to as "monomer".
In the method for producing the copolymer of the present disclosure, copolymerization may also be applied in the presence of a polymerization initiator. As the polymerization initiator, conventional or publicly known radical polymerization initiators can be used, and examples thereof include: azo compounds such as 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl-2, 2' -azobis (2-methylpropionate), diethyl-2, 2 '-azobis (2-methylpropionate), and dibutyl-2, 2' -azobis (2-methylpropionate); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, and 1, 1-bis (t-butylperoxy) cyclohexane; hydrogen peroxide, and the like. When a peroxide is used as the radical polymerization initiator, a redox type initiator may be prepared by combining a reducing agent. Among them, azo compounds are preferable, and 2,2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), dimethyl-2, 2' -azobis (2-methylpropionate) are more preferable.
The amount of the polymerization initiator to be used may be appropriately selected within a range not hindering smooth copolymerization, and is not particularly limited, and is, for example, preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on the total amount (100 parts by weight) of the monomers.
In the present disclosure, the copolymerization can be carried out by a conventional method used for producing an acrylic polymer or a styrene polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, or emulsion polymerization. The monomer and the polymerization initiator may be supplied to the reaction system at once, or a part or all of them may be added dropwise to the reaction system. For example, the following method may be employed: a method of polymerizing a monomer or a mixture of a monomer and a polymerization solvent, which is maintained at a predetermined temperature, by dropping a solution obtained by dissolving a polymerization initiator in the polymerization solvent; a method of performing polymerization by dropping a solution prepared by dissolving a monomer and a polymerization initiator in a polymerization solvent in advance into a polymerization solvent maintained at a certain temperature (dropping polymerization method), and the like.
The copolymer in the present disclosure is preferably copolymerized in a polymerization solvent. The polymerization solvent may be appropriately selected depending on the monomer composition, and examples thereof include: ethers (diethyl ether; ethylene glycol mono-or dialkyl ether, diethylene glycol mono-or dialkyl ether, propylene glycol mono-or diaryl ether, dipropylene glycol mono-or dialkyl etherChain ethers such as glycol ethers including tripropylene glycol mono-or dialkyl ether, 1, 3-propanediol mono-or dialkyl ether, 1, 3-butanediol mono-or dialkyl ether, 1, 4-butanediol mono-or dialkyl ether, and glycerol mono-, di-or trialkyl ether; cyclic ether such as tetrahydrofuran and dioxane), ester (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C 5-6 Cycloalkane diol Mono or diacetate, C 5-6 Carboxylic acid esters such as cyclohexanedimethanol mono-or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono-or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono-or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono-or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono-or diacetate, 1, 3-propylene glycol monoalkyl ether acetate, 1, 3-propylene glycol mono-or diacetate, 1, 3-butylene glycol monoalkyl ether acetate, 1, 3-butylene glycol mono-or diacetate, 1, 4-butylene glycol monoalkyl ether acetate, 1, 4-butylene glycol mono-or diacetate, glycerol mono-, di-or triacetate, glycerol mono-or di-C 1-4 Glycol acetates such as alkyl ether di-or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono-or diacetate, and glycol ether acetates), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3, 5-trimethyl-2-cyclohexen-1-one, and the like), amides (N, N-dimethylacetamide, N-dimethylformamide, and the like), sulfoxides (dimethyl sulfoxide, and the like), alcohols (methanol, ethanol, propanol, C-dimethyl formamide, and the like), and the like 5-6 Cycloalkane diol, C 5-6 Cycloalkanedimethanol, etc.), hydrocarbons (aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as hexane, etc., alicyclic hydrocarbons such as cyclohexane, etc.), mixed solvents thereof, and the like.
The polymerization temperature may be appropriately selected depending on the kind and composition of the monomer, and is not particularly limited, and is, for example, preferably 30 to 150 ℃.
The reaction solution containing the copolymer obtained by the above-mentioned method may be purified by carrying out precipitation or reprecipitation as needed. The solvent used for the precipitation or reprecipitation may be any of an organic solvent and water, and may be a mixed solvent thereof. Examples of the organic solvent include: hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene); halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, and the like); nitro compounds (nitromethane, nitroethane, etc.); nitriles (acetonitrile, benzonitrile, and the like), ethers (chain ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, and the like; cyclic ethers such as tetrahydrofuran, dioxane, and the like); ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.); esters (ethyl acetate, butyl acetate, etc.); carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.); alcohols (methanol, ethanol, propanol, isopropanol, butanol, etc.); carboxylic acids (acetic acid, etc.); and mixed solvents containing these solvents.
< color Material >
In the present disclosure, the coloring material (colorant) may be any material as long as it has colorability, and the color and material may be appropriately selected according to the application such as a color filter. Specifically, any of pigments, dyes, and natural pigments can be used as the color material, but pigments and/or dyes are preferable because high color purity, brightness, contrast, and the like are required for color filter applications.
The pigment may be any of organic pigments and inorganic pigments, and examples of The organic pigment include compounds classified as pigments (pigments) in The color index (c.i.; issued by The Society of Dyers and Colourists). Specifically, pigments to which a color index (c.i.) name is added as described below can be cited.
C.i. pigment yellow 1, c.i. pigment yellow 3, c.i. pigment yellow 12, c.i. pigment yellow 13, c.i. pigment yellow 14, c.i. pigment yellow 16, c.i. pigment yellow 17, c.i. pigment yellow 20, c.i. pigment yellow 24, c.i. pigment yellow 31, c.i. pigment yellow 55, c.i. pigment yellow 83, c.i. pigment yellow 86, c.i. pigment yellow 93, c.i. pigment yellow 94, c.i. pigment yellow 109, c.i. pigment yellow 110, c.i. pigment yellow 117, c.i. pigment yellow 125, c.i. pigment yellow 137, c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 147, c.i. pigment yellow 148, c.i. pigment yellow 150, c.i. pigment yellow 153, c.i. pigment yellow 154, c.i. pigment yellow 155, c.i. pigment yellow 166, c.i. pigment yellow 214, c.i. pigment yellow 168, c.i. pigment yellow 214, c.i. pigment yellow 83, c.i. pigment yellow.
Orange pigments such as c.i. pigment orange 5, c.i. pigment orange 13, c.i. pigment orange 14, c.i. pigment orange 24, c.i. pigment orange 31, c.i. pigment orange 34, c.i. pigment orange 36, c.i. pigment orange 38, c.i. pigment orange 40, c.i. pigment orange 42, c.i. pigment orange 43, c.i. pigment orange 46, c.i. pigment orange 49, c.i. pigment orange 51, c.i. pigment orange 55, c.i. pigment orange 59, c.i. pigment orange 61, c.i. pigment orange 64, c.i. pigment orange 65, c.i. pigment orange 68, c.i. pigment orange 70, c.i. pigment orange 71, c.i. pigment orange 72, c.i. pigment orange 73, c.i. pigment orange 74, and the like.
C.i. pigment red 1, c.i. pigment red 2, c.i. pigment red 5, c.i. pigment red 9, c.i. pigment red 17, c.i. pigment red 31, c.i. pigment red 32, c.i. pigment red 41, c.i. pigment red 97, c.i. pigment red 105, c.i. pigment red 122, c.i. pigment red 123, c.i. pigment red 144, c.i. pigment red 149, c.i. pigment red 166, c.i. pigment red 168, c.i. pigment red 170, c.i. pigment red 171, c.i. pigment red 175, c.i. pigment red 176, c.i. pigment red 177, c.i. pigment red 178, c.i. pigment red 179 red pigments such as c.i. pigment red 180, c.i. pigment red 185, c.i. pigment red 187, c.i. pigment red 192, c.i. pigment red 202, c.i. pigment red 206, c.i. pigment red 207, c.i. pigment red 209, c.i. pigment red 214, c.i. pigment red 215, c.i. pigment red 216, c.i. pigment red 220, c.i. pigment red 221, c.i. pigment red 224, c.i. pigment red 242, c.i. pigment red 243, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment red 262, c.i. pigment red 264, c.i. pigment red 265, and c.i. pigment red 272.
Violet pigments such as c.i. pigment violet 1, c.i. pigment violet 19, c.i. pigment violet 23, c.i. pigment violet 29, c.i. pigment violet 32, c.i. pigment violet 36 and c.i. pigment violet 38.
C.i. pigment blue 15, c.i. pigment blue 15: 3. c.i. pigment blue 15: 4. c.i. pigment blue 15: 6. blue pigments such as c.i. pigment blue 60 and c.i. pigment blue 80.
Green pigments such as c.i. pigment green 7, c.i. pigment green 36, and c.i. pigment green 58.
Brown pigments such as c.i. pigment brown 23 and c.i. pigment brown 25.
Black pigments such as c.i. pigment black 1 and c.i. pigment black 7.
Examples of the inorganic pigment include: titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, umber (umber), titanium black, synthetic iron black, carbon black, and the like.
In the present disclosure, the pigment may also be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. Further, the pigment may be used by modifying the particle surface with a resin.
The dye may be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like, and examples thereof include dyes given the color index (c.i.) name described below.
Yellow dyes such as c.i. solvent yellow 4, c.i. solvent yellow 14, c.i. solvent yellow 15, c.i. solvent yellow 24, c.i. solvent yellow 82, c.i. solvent yellow 88, c.i. solvent yellow 94, c.i. solvent yellow 98, c.i. solvent yellow 162, c.i. solvent yellow 179, c.i. acid yellow 17, c.i. acid yellow 29, c.i. acid yellow 40, and c.i. acid yellow 76.
Orange dyes such as c.i. solvent orange 2, c.i. solvent orange 7, c.i. solvent orange 11, c.i. solvent orange 15, c.i. solvent orange 26, c.i. solvent orange 56, c.i. acid orange 51, and c.i. acid orange 63.
Red dyes such as c.i. solvent red 45, c.i. solvent red 49, c.i. acid red 91, c.i. acid red 92, c.i. acid red 97, c.i. acid red 114, c.i. acid red 138, and c.i. acid red 151.
Blue dyes such as c.i. solvent blue 35, c.i. solvent blue 37, c.i. solvent blue 59, c.i. solvent blue 67, c.i. acid blue 80, c.i. acid blue 83, and c.i. acid blue 90.
Green dyes such as c.i. acid green 9, c.i. acid green 16, c.i. acid green 25, and c.i. acid green 27.
In the present disclosure, the color materials may be used alone or in combination of two or more.
The content of the color material with respect to the solid content of the photosensitive resin composition is not particularly limited, and is, for example, preferably 3 to 50% by weight, and more preferably 5to 30% by weight. The "solid component" herein means, for example, a component other than the above-mentioned solvent.
In the present disclosure, when a pigment is used as the color material, the pigment may be used together with a pigment dispersant and a pigment dispersion aid as desired. Examples of the pigment dispersant include: cationic, anionic, nonionic, amphoteric and other dispersants (surfactants); and polymer dispersants such as acrylic copolymers, polyesters, polyurethanes, polyethyleneimines, and polyallylamines.
As the pigment dispersant, commercially available pigment dispersants can be used, and examples thereof include: disperbyk-2000, disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (BYK Chemie (BYK) Co., ltd.) as acrylic copolymers; ajispper PB821, ajispper PB822, and Ajispper PB880 (manufactured by Ajinomoto Fine-Techno Co., ltd.) as polyesters; examples of the polyurethane include Disperbyk-161, disperbyk-162, disperbyk-165, disperbyk-167, disperbyk-170, disperbyk-182 (BYK Chemie (BYK) Co., ltd.), solsperse 76500 (Lubrizol corporation); solsperse 24000 (manufactured by Lubrizol corporation) as polyethyleneimine, and the like.
These pigment dispersants may be used alone or in admixture of two or more. The content of the pigment dispersant is usually not more than 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 10 to 70 parts by weight, and further preferably 30 to 60 parts by weight, based on 100 parts by weight of the pigment. When the content of the pigment dispersant is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained, and therefore, the content is preferable.
Examples of the pigment dispersion aid include pigment derivatives, and specifically, include: sulfonic acid derivatives of copper phthalocyanine, pyrrolopyrroledione, quinophthalone, and the like. The content of the pigment dispersing aid may be appropriately determined within a range not interfering with the object of the invention of the present disclosure.
< photopolymerizable Compound >
In the present disclosure, the photopolymerizable compound is not particularly limited, and examples thereof include: a polyfunctional vinyl compound, a polyfunctional thiol compound, and a polyfunctional epoxy compound.
The polyfunctional vinyl compound is not particularly limited as long as it is a compound having two or more vinyl groups, and examples thereof include: di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; di (meth) acrylates of two-terminal hydroxylated polymers such as two-terminal hydroxyl polybutadiene, two-terminal hydroxyl polyisoprene, two-terminal hydroxyl polycaprolactone, and the like; poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerol, 1,2, 4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol and the like; poly (meth) acrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols; poly (meth) acrylates of cyclic polyols such as 1, 4-cyclohexanediol and 1, 4-benzenediol; and oligomeric (meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and silicone (meth) acrylate. Among these, polyfunctional (meth) acrylates having two or more (meth) acryloyl groups are preferred. The polyfunctional vinyl compounds may be used alone or in combination of two or more.
The polyfunctional thiol compound is not particularly limited as long as it has two or more thiol groups, and examples thereof include: hexanedithiol, decanedithiol, 1, 4-butanediol dithiopropionate, 1, 4-butanediol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1, 4-dimethylmercaptobenzene, 2,4, 6-trimercaptos-triazine, 2- (N, N-dibutylamino) -4, 6-dimercaptos-s-triazine, tetraethyleneglycol bis 3-mercaptopropionate, trimethylolpropane tris 3-mercaptopropionate, tris (3-mercaptopropynyloxyethyl) isocyanurate, pentaerythritol tetrakis 3-mercaptopropionate, dipentaerythritol tetrakis 3-mercaptopropionate, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H) -triketone, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. The polyfunctional thiol compound may be used alone or in combination of two or more.
The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups, and examples thereof include: glycidyl ether type epoxy compound [ glycidyl ether produced by the reaction of a polyhydric compound (bisphenol, polyphenol, alicyclic polyol, aliphatic polyol, etc.) with epichlorohydrin (for example, (poly) C such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc.) 2-4 Alkylene glycol diglycidyl ether; diglycidyl ethers of polyphenols such as resorcinol and hydroquinone; diglycidyl ethers of alicyclic polyols such as cyclohexanediol, cyclohexanedimethanol and hydrogenated bisphenols; bisphenols (e.g. bis (hydroxyphenyl) alkanes such as 4,4' -dihydroxybiphenyl and bisphenol A) and C thereof 2-3 Diglycidyl ether of alkylene oxide adduct, etc.), phenol novolac type epoxy resin (phenol novolac type or cresol novolac type epoxy resin, etc.), etc](ii) a Glycidyl ester type epoxy compounds; alicyclic epoxy compounds (or cyclic aliphatic epoxy resins); heterocyclic epoxy resins (triglycidyl isocyanurate (TGIC); hydantoin type epoxy resins, etc.); glycidyl amine type epoxy compounds [ reaction products of amines and epichlorohydrin, for example, N-glycidyl aromatic amines { tetraglycidyl diaminodiphenylmethane (TGDDM), triglycidyl aminophenol (triglycidyl-p-aminophenol (TGPAP), triglycidyl-m-aminophenol (TGMAP), etc.), diglycidylaniline (DGA), diglycidyltoluidine (DGT), tetraglycidyl xylylenediamine (tetraglycidyl-m-xylylenediamine (TGMXA), etc.) }, N-glycidyl alicyclic amines (tetraglycidyl bisaminocyclohexane, etc.), etc]And the like. Multiple purposeThe functional epoxy compounds may be used alone or in combination of two or more.
The photopolymerizable compounds may be used alone or in combination of two or more. The content of the photopolymerizable compound is usually 10 to 300 parts by weight, preferably 30 to 200 parts by weight, and more preferably 40 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the photosensitive resin composition contains a color material, the content of the photopolymerizable compound is usually 10 to 1000 parts by weight, preferably 50 to 600 parts by weight, and more preferably 100 to 500 parts by weight, based on 100 parts by weight of the color material. When the content of the photopolymerizable compound is within the above range, curing is sufficiently performed, and good adhesion can be obtained.
< photopolymerization initiator >
In the present disclosure, the photopolymerization initiator is not particularly limited, and examples thereof include: a photo radical polymerization initiator and a photo cation polymerization initiator.
The photo radical polymerization initiator is a compound that generates radicals by irradiation with light to initiate a curing reaction (radical polymerization) of a photopolymerizable compound contained in the photosensitive resin composition. The photo radical polymerization initiator may be used alone or in combination of two or more.
Examples of the photo radical polymerization initiator include: thioxanthone compounds, acetophenone compounds, bisimidazole compounds, triazine compounds, oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -diketone compounds, polyquinone compounds, diazo compounds, imide sulfonate compounds, anthracene compounds, and the like.
Examples of the thioxanthone compound include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of the acetophenone-based compound include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethyl ketal (Benzil dimethyl ketone), 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-dimethylamino-1- (4-morpholinophenyl) -butanone ) -butanone, 2- (2, 3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2, 4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone Oligomers of 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one.
Examples of the bisimidazole compound include: 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole, an imidazole compound obtained by substituting phenyl group at the 4,4'5,5' -position with alkoxycarbonyl group, and the like.
Examples of the triazine-based compound include: 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, etc.
Examples of the oxime compound include O-ethoxycarbonyl- α -hydroxyimino-phenylpropan-1-one.
Examples of the benzoin-based compound include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
Examples of the benzophenone-based compound include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 '-methyldiphenylsulfide, 3',4 ≡ tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, and the like.
Examples of the anthracene compound include: 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, etc.
The photo cation polymerization initiator is a compound that generates an acid by irradiation with light to initiate a curing reaction (cation polymerization) of a photopolymerizable compound contained in the photosensitive resin composition, and includes a cation portion that absorbs light and an anion portion that is a generation source of the acid. The photo cation polymerization initiator may be used alone or in combination of two or more.
Examples of the photo cation polymerization initiator include: diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, and the like.
Examples of the anionic portion of the photo cation polymerization initiator include: [ (Y) s B(Phf) 4-s ] - (wherein Y represents a phenyl group or a biphenyl group, phf represents a phenyl group in which at least one of hydrogen atoms is substituted by at least one member selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom, s is an integer of 0 to 3), BF 4 - 、[(Rf) k PF 6-k ] - (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and k: an integer of 0 to 5), asF 6 - 、SbF 6 - 、SbF 5 OH - And so on.
Examples of the photo cation polymerization initiator include: (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylthio) phenyl-4-biphenylphenylsulfinyltetrakis (pentafluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylthio) phenyl ] -4-biphenylphenylsulfinylphenyltris (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl ] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl ] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl ] sulfonium hexafluorophosphate, 4- (4-biphenylthio) phenyl-4-biphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonium) phenyl ] phenyl tris (pentafluorophenyl) borate, [4- (2-thioxanthenylthio) phenyl ] phenyl-2-thioxanthenylsulfonium phenyl tris (pentafluorophenyl) borate, 4- (phenylthio) phenyl diphenylsulfonium hexafluoroantimonate, and the like.
As the photo cation polymerization initiator, there can be used: trade names of "CyracureUVI-6970", "CyracureUVI-6974", "CyracureUVI-6990" and "CyracureUVI-950" (manufactured by Union Carbide, USA); "Irgacure250", "Irgacure261", "Irgacure264" (manufactured by BASF corporation); "CG-24-61" (manufactured by Ciba Geigy Co.); "OptomersP-150", "OptomersP-151", "OptomersP-170", "OptomersP-171" (manufactured by ADEKA strain, supra); "DAICAT II" ((strain) manufactured by DAICEL); "UVAC1590" and "UVAC1591" (manufactured by DAICEL-Cytec Co., ltd.); "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758" and "CIT-1682" (manufactured by Nippon Caoda corporation); "PI-2074" (tolylcumylium tetrakis (pentafluorophenyl) borate, manufactured by Rhodia); "FFC509" (manufactured by 3M Co., ltd.); "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (manufactured by Midori chemical Co., ltd.); "CD-1010", "CD-1011" and "CD-1012" (manufactured by Sartomer, U.S.A.); commercially available products such as "CPI-100P" and "CPI-101A" (manufactured by San-Apro, inc., supra).
The content of the photopolymerization initiator (the total amount thereof in the case of two or more types) is, for example, 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably 3 to 20 parts by weight, based on 100 parts by weight of the photopolymerizable compound (the total amount) contained in the photosensitive resin composition. If the content of the photopolymerization initiator is less than the above range, curability tends to decrease. On the other hand, if the content of the photopolymerization initiator exceeds the above range, the cured product tends to be easily colored.
< solvent >
Examples of the solvent include: ethers (e.g., linear ethers such as glycol ethers including diethyl ether, ethylene glycol mono-or dialkyl ether, diethylene glycol mono-or dialkyl ether, propylene glycol mono-or diaryl ether, dipropylene glycol mono-or dialkyl ether, tripropylene glycol mono-or dialkyl ether, 1, 3-propanediol mono-or dialkyl ether, 1, 3-butanediol mono-or dialkyl ether, 1, 4-butanediol mono-or dialkyl ether, and glycerol mono-, di-or trialkyl ether), cyclic ethers such as tetrahydrofuran and dioxane, and the like); esters (acetic acid) methyl ester ethyl acetate,Butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C 5-6 Cycloalkane diol mono-or diacetate, C 5-6 Carboxylic acid esters such as cyclohexanedimethanol mono-or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono-or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono-or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono-or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono-or diacetate, 1, 3-propylene glycol monoalkyl ether acetate, 1, 3-propylene glycol mono-or diacetate, 1, 3-butylene glycol monoalkyl ether acetate, 1, 3-butylene glycol mono-or diacetate, 1, 4-butylene glycol monoalkyl ether acetate, 1, 4-butylene glycol mono-or diacetate, glycerol mono-, di-or triacetate, glycerol mono-or di-C 1-4 Glycol acetates such as alkyl ether di-or monoacetate, tripropylene glycol mono-alkyl ether acetate, tripropylene glycol mono-or diacetate, and glycol ether acetates); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3, 5-trimethyl-2-cyclohexen-1-one, etc.), and the like. These solvents may be used alone or in combination of two or more.
The photosensitive resin composition of the present disclosure may contain, in addition to the above components, for example, resins such as novolac resin, phenol resin, imide resin, and carboxyl group-containing resin; a curing agent; a curing accelerator; additives (fillers, antifoaming agents, flame retardants, antioxidants, ultraviolet absorbers, colorants, stress reducers, flexibility imparting agents, waxes, resins, crosslinking agents, halogen trap (halogen trap) agents, leveling agents, wettability improving agents, and the like).
The concentration of the alkali-soluble resin in the photosensitive resin composition of the present disclosure is not particularly limited, and is, for example, 2 to 60% by weight, preferably 5to 30% by weight.
As a method for producing the photosensitive resin composition of the present disclosure, for example, the following methods can be cited: and a method of dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives as necessary in a solvent.
When the photosensitive resin composition of the present disclosure contains a color material, examples of a method for producing the photosensitive resin composition include the following methods: a method in which a pigment dispersant is optionally present in a solvent to disperse a color material such as a pigment to prepare a color material dispersion liquid, and an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and if necessary, other additives are dissolved in a solvent, and the mixture is mixed with the color material dispersion liquid, and if necessary, a solvent is further added.
The photosensitive resin composition of the present disclosure is usually sealed in a container for distribution and storage. The photosensitive resin composition of the present disclosure has excellent storage stability during distribution and storage.
< cured product >
By curing the photosensitive resin composition of the present disclosure, a cured product having excellent various physical properties can be obtained. For example, a cured product can be obtained by applying the photosensitive resin composition to various substrates or substrates by a conventional application unit such as a spin coater, a dip coater, a roll coater, or a slit coater to form a coating film and then curing the coating film. The curing is performed by, for example, applying light irradiation and/or heat treatment to the photosensitive resin composition.
The light irradiation is performed using, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, an LED light source, or the like, and the cumulative dose is preferably 500 to 5000mJ/cm 2 Is irradiated within the range of (1).
Preferably, the heat treatment is performed, for example, at a temperature of 60 to 300 ℃ (preferably 100 to 250 ℃), for example, for 1 to 120 minutes (preferably 1 to 60 minutes).
Examples of the substrate or substrate include: silicon wafers, metals, plastics, glass, ceramics, etc. The thickness of the cured coating film is, for example, preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm.
The cured product (cured coating film) of the present disclosure has excellent solvent resistance and high insulation properties, and is therefore useful as a protective film (color filter protective film, etc.), an insulating film, a material for forming microlenses, or the like.
< color Filter >
The color filter of the present disclosure is a cured product of the photosensitive resin composition of the present disclosure. The color filter of the present disclosure may also include a colored pattern formed from the photosensitive resin composition. The color filter can be manufactured, for example, by the following steps: forming a colored pattern on a substrate using the photosensitive resin composition; and post-baking (post-make) the colored pattern.
Examples of the method for forming a pattern of a color filter using the photosensitive resin composition of the present disclosure include the following methods: a method in which the photosensitive resin composition of the present disclosure is applied onto a substrate or another resin layer by a conventional application unit such as a spin coater, a colored layer is formed by removing volatile components such as a solvent, and the colored layer is exposed and developed through a photomask.
Examples of the substrate include: and flat-surface substrates such as glass substrates, silicone substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, polyimide substrates, al substrates, and GaAs substrates. These substrates may be subjected to pretreatment such as reagent treatment with a reagent such as a silane coupling agent, plasma treatment, ion plating (ion plating), sputtering, vapor reaction treatment, or vacuum deposition treatment.
The thickness of the dried colored layer is, for example, 0.6 to 8 μm, preferably 1 to 5 μm.
Examples of the light source of the radiation used for exposure include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps; and laser light sources such as argon ion laser, YAG laser, xeCl excimer laser, and nitrogen laser. The wavelength of the radiation is preferably in the range of 190 to 450 nm. The exposure amount of the radiation is preferably 10 to 10000J/m in general 2 。
As the alkali developing solution used for the development, for example, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1, 8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene, etc. is preferable.
The postbaking conditions are usually about 10 to 60 minutes at 120 to 280 ℃. The thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.
According to the photosensitive resin composition disclosed by the disclosure, a colored pattern which is excellent in curing reactivity and has sufficient solvent resistance can be obtained.
< Member for display device or display device >
The member for a display device or the display device of the present disclosure includes the color filter. Examples of the member for a display device include a color liquid crystal display element. In addition, as the display device, for example, a color liquid crystal display device can be cited. The color liquid crystal display element and the color liquid crystal display are not particularly limited in structure, and may have an appropriate structure.
It should be noted that the various aspects disclosed in this specification may be combined with any other feature disclosed in this specification. The respective configurations and combinations thereof in the respective embodiments are examples, and addition, omission, and other modifications of the configurations may be appropriately made within the scope not departing from the gist of the present invention. The present disclosure is not to be limited by the embodiments, but only by the claims.
Examples
Hereinafter, the present disclosure will be described in further detail based on examples.
The weight average molecular weight (in terms of polystyrene) and the dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the copolymer were measured under the following conditions.
The device comprises the following steps: a detector: RID-20A (Shimadzu corporation).
A pump: LC-20AD (Shimadzu corporation).
A system controller: CBM-20Alite (Shimadzu Corp.).
A degassing device: DGU-20A3 (Shimadzu corporation).
An autosampler: SIL-20A HT (Shimadzu corporation).
A chromatographic column: shodex KF-806L (Showa Denko K.K.).
Eluent: THF (tetrahydrofuran) 0.8ml/min.
Temperature: baking oven: 40 ℃, RI: at 40 ℃.
A detector: and RI.
The exothermic peak top temperature was measured by the following method. That is, 5g of the copolymer-containing solutions obtained in production examples 1 to 8 was added dropwise to 50g of heptane with stirring. The resulting precipitate was separated by filtration and dried under reduced pressure to obtain a copolymer in the form of a white powder. About 10mg of the white powder was used as a sample, and the temperature of the exothermic peak was measured by raising the temperature from 40 ℃ to 300 ℃ at a rate of 5 ℃/min under a nitrogen atmosphere using a differential scanning calorimeter (DSC 1, manufactured by Mettler Toledo).
Reference example 1 preparation of monomer B1
A mixed solution of 33.7g of 5-norbornene-2-methanol, 41.3g of triethylamine and 6.5mg of p-methoxyphenol in 57.2g of THF (tetrahydrofuran) was added thereto, 42.4g of methacryloyl chloride was added dropwise over 40 minutes while maintaining the internal temperature at 20 ℃ or lower, and then the mixture was stirred at 20 ℃ for 4 hours. After confirming the disappearance of 5-norbornene-2-methanol as a raw material by gas chromatography, 100g of acetic ether and 84.0g of water were added. After the liquid separation, the resultant was washed with 94.8g of a 10% aqueous sodium hydroxide solution and three times with 68.0g of water. The resulting organic phase was concentrated at 40 ℃ and 15Torr, whereby 48.3g of a crude product of 5-norbornene-2-methyl acrylate was obtained. The crude product was 93% pure and 86% yield.
To a mixed solution of the crude product of 5-norbornene-2-methyl acrylate (47.5 g) and p-methoxyphenol (9.4 mg) in ethyl acetate (141 g) was added 72.3g of mCPBA (3-chloroperoxybenzoic acid, containing 30% water) over 1 hour while maintaining the internal temperature at 20 ℃ or lower, and then the mixture was stirred at 20 ℃ for 3 hours. After confirming the disappearance of the starting material by gas chromatography, 278g of a 15% aqueous sodium thiosulfate solution and 141g of ether acetate were added and stirred for 15 minutes. After the liquid separation, the resultant was washed with 217g of an 8% aqueous sodium bicarbonate solution and twice with 141g of water. Concentrating the organic phase, purifying by silica gel column chromatographyThis gives 29.4g of 3-oxatricyclo [3.2.1.0 ] methacrylate 2,4 ]Octane-6-ylmethyl ester (hereinafter, sometimes referred to as "monomer B1"). Methacrylic acid 3-oxatricyclo [3.2.1.0 2,4 ]The purity of the octane-6-ylmethyl ester was 99% and the yield was 71%.
Production example 1
A proper amount of nitrogen was blown into a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and 150 parts by weight of propylene glycol monomethyl ether acetate was charged into the flask in a nitrogen atmosphere and heated to 80 ℃ with stirring. Then, 7 parts by weight of 2,2' -Azobisisobutyronitrile (AIBN) was added while washing with 30 parts by weight of propylene glycol monomethyl ether acetate. Next, a mixed solution of 11 parts by weight of Acrylic Acid (AA) and 89 parts by weight of monomer B1 and 20 parts by weight of propylene glycol monomethyl ether acetate as monomers was added dropwise to the flask over about 4 hours using a dropping pump. After completion of the dropwise addition of the monomers, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer-containing solution having a solid content of 34.6% by weight. The weight average molecular weight Mw of the resulting copolymer was 19000 and the dispersity was 3.47.
Production example 2
A copolymer-containing solution having a solid content of 33.8 wt% was obtained by performing the same operation as in production example 1, except that 11 parts by weight of Acrylic Acid (AA), 79 parts by weight of the monomer B1, and 10 parts by weight of Styrene (ST) were used as monomers. The weight average molecular weight Mw of the resulting copolymer was 17000 and the dispersity was 3.33.
Production example 3
A copolymer-containing solution having a solid content of 34.2 wt% was obtained in the same manner as in production example 1, except that 11 parts by weight of Acrylic Acid (AA), 79 parts by weight of the monomer B1, and 10 parts by weight of Methyl Methacrylate (MMA) were used as monomers. The weight-average molecular weight Mw of the resulting copolymer was 18500 and the dispersity was 3.41.
Production example 4
A copolymer-containing solution having a solid content of 34.4 wt% was obtained in the same manner as in production example 1, except that 11 parts by weight of Acrylic Acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of Cyclohexylmaleimide (CHMI) were used as monomers. The weight average molecular weight Mw of the resulting copolymer was 18000 and the dispersity was 3.40.
Production example 5
A copolymer-containing solution having a solid content of 34.4 wt% was obtained by performing the same operation as in production example 1, except that 11 parts by weight of Acrylic Acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of N-Vinylpyrrolidone (VP) were used as monomers. The weight average molecular weight Mw of the resulting copolymer was 17500 and the dispersity was 3.38.
Production example 6
An appropriate amount of nitrogen was blown into a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and 150 parts by weight of propylene glycol monomethyl ether acetate was added under a nitrogen atmosphere and heated to 65 ℃ with stirring. Then, 14 parts by weight of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added while washing with 30 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, a solution prepared by dissolving 11 parts by weight of Acrylic Acid (AA), 79 parts by weight of Glycidyl Methacrylate (GMA), and 10 parts by weight of Methyl Methacrylate (MMA), which are monomers, in 20 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the flask using a dropping pump over about 4 hours. After completion of the dropwise addition of the monomers, the mixture was kept at the same temperature for about 4 hours and then cooled to room temperature to obtain a copolymer-containing solution having a solid content of 33.8% by weight. The weight-average molecular weight Mw of the resulting copolymer was 16000, and the dispersity was 3.32.
Production example 7
A copolymer-containing solution having a solid content of 33.4 wt% was obtained in the same manner as in production example 6, except that 11 parts by weight of Acrylic Acid (AA), 79 parts by weight of 3, 4-epoxycyclohexylmethyl methacrylate (cyclomer m 100) and 10 parts by weight of Methyl Methacrylate (MMA) were used as monomers. The weight average molecular weight Mw of the resulting copolymer was 16000 and the dispersity was 3.30.
Production example 8
Using 11 parts by weight of propyleneOlefine acid (AA), 89 weight portions of 3, 4-epoxy tricyclo [5.2.1.0 ] acrylic acid 2,6 ]Decane-9-yl ester with acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]A copolymer-containing solution having a solid content of 34.1% by weight was obtained in the same manner as in production example 1, except that the mixture of decane-8-yl ester (monomer B2) was used as a monomer. The weight-average molecular weight Mw of the resulting copolymer was 18000, and the dispersity was 3.43.
The compositions of the copolymers, the weight-average molecular weights, the degrees of dispersion and the peak temperatures of heat release in production examples 1 to 8 are shown in Table 1.
[ example 1-1]
In a container, 8.09g of a copolymer-containing solution prepared from the copolymer obtained in production example 1 as an alkali-soluble resin, 2.25g of DPHA as a photopolymerizable compound, 0.20g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and 6.83g of MMPGAC6 as a solvent were weighed and stirred for 30 minutes, thereby preparing a photosensitive resin composition 1-1.
[ examples 1-2]
A photosensitive resin composition 1-2 was prepared in the same manner as in example 1-1 except that 8.09g of the copolymer-containing solution prepared in production example 2, which was an alkali-soluble resin, was used.
[ examples 1 to 3]
Photosensitive resin compositions 1 to 3 were prepared in the same manner as in example 1 to 1, except that 8.09g of the copolymer-containing solution prepared in production example 3, which was an alkali-soluble resin, was used.
[ examples 1 to 4]
Photosensitive resin compositions 1 to 4 were prepared in the same manner as in example 1 to 1, except that 8.09g of the copolymer-containing solution prepared in production example 4, which was an alkali-soluble resin, was used.
[ examples 1 to 5]
Photosensitive resin compositions 1 to 5 were prepared in the same manner as in example 1 to 1, except that 8.09g of the copolymer-containing solution prepared in production example 5, which was an alkali-soluble resin, was used.
Comparative examples 1 to 1
Photosensitive resin compositions 1 to 6 were prepared in the same manner as in example 1 to 1, except that 8.09g of the copolymer-containing solution prepared in production example 6, which was an alkali-soluble resin, was used.
Comparative examples 1 and 2
Photosensitive resin compositions 1 to 7 were prepared in the same manner as in example 1 to 1 except that 8.09g of the copolymer-containing solution prepared in production example 7 as the alkali-soluble resin was used.
Comparative examples 1 to 3
Photosensitive resin compositions 1 to 8 were prepared in the same manner as in example 1 to 1 except that 8.09g of the copolymer-containing solution obtained in production example 8 as the alkali-soluble resin was used.
The compositions of the photosensitive resin compositions of the examples and comparative examples are shown in table 2.
[ example 2-1]
In a container, 7.7g of pigment C.I. pigment Red 254 as a color material, 3.1g of DISPERBYK-2000 as a dispersant, and 36.0g of MMPGAC as a solvent were weighed, and 45g of zirconia beads having a diameter of 1.0mm were further added, and the container was covered with a lid. This was shaken with a paint shaker (paint shaker) for 3 hours, after which the pigment dispersion was separated from the zirconia beads, 45g of 0.5mm zirconia beads were added, and further shaken with a paint shaker for 3 hours. Then, the pigment dispersion liquid was separated from the zirconia beads, 45g of 0.3mm zirconia beads were added, and after further shaking for 3 hours with a paint shaker, the zirconia beads were separated to obtain a pigment dispersion liquid.
With respect to 4.68g of the obtained pigment dispersion, 8.09g of a copolymer-containing solution prepared from the copolymer obtained in production example 1 as an alkali-soluble resin, 2.25g of DPHA as a photopolymerizable compound, 0.20g of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and 15.2g of MMPGAC15 as a solvent were weighed out in a container and stirred for 30 minutes, thereby preparing a photosensitive resin composition 2-1.
[ example 2-2]
A photosensitive resin composition 2-2 was prepared in the same manner as in example 2-1 except that 8.09g of the copolymer-containing solution prepared in production example 2, which was an alkali-soluble resin, was used.
[ examples 2 to 3]
A photosensitive resin composition 2-3 was prepared in the same manner as in example 2-1 except that 8.09g of the copolymer-containing solution prepared in production example 3 above was used as the alkali-soluble resin.
[ examples 2 to 4]
A photosensitive resin composition 2-4 was prepared in the same manner as in example 2-1, except that 8.09g of the copolymer-containing solution prepared in production example 4, which was an alkali-soluble resin, was used.
[ examples 2 to 5]
A photosensitive resin composition 2-5 was prepared in the same manner as in example 2-1 except that 8.09g of the copolymer-containing solution prepared in production example 5, which was an alkali-soluble resin, was used.
Comparative example 2-1
A photosensitive resin composition 2-6 was prepared in the same manner as in example 2-1 except that 8.09g of the copolymer-containing solution prepared in production example 6, which was an alkali-soluble resin, was used.
Comparative examples 2 and 2
A photosensitive resin composition 2-7 was prepared in the same manner as in example 2-1, except that 8.09g of a copolymer-containing solution prepared in production example 7, which was an alkali-soluble resin, was used.
Comparative examples 2 to 3
A photosensitive resin composition 2-8 was prepared in the same manner as in example 2-1 except that 8.09g of the copolymer-containing solution obtained in production example 8 as the alkali-soluble resin was used.
The compositions of the photosensitive resin compositions of the examples and comparative examples are shown in Table 4.
< evaluation test >
The following evaluation tests were carried out using the photosensitive resin compositions obtained in examples 1-1 to 1-5 and comparative examples 1-1 to 1-3. The results are shown in Table 3.
(1) Storage stability test 1
The photosensitive resin compositions obtained in examples 1-1 to 1-5 and comparative examples 1-1 to 1-3 were stored in an oven at 40 ℃ for one week. The viscosity immediately after polymerization and the viscosity after storage at 40 ℃ for one week were measured. The viscosity increase rate was calculated according to the following calculation formula. The viscosity (unit: mPas) was measured at a rotation speed of 60 and a temperature of 60 ℃ using a viscometer (trade name "LVDV2T", manufactured by Brookfield Co., ltd.): measured at 23 ℃.
P: viscosity immediately after polymerization, Q: viscosity after storage at 40 ℃ for one week.
Viscosity increase rate = { (Q/P) × 100} -100.
(2) Solvent resistance test-1
Test pieces were prepared by applying the photosensitive resin compositions obtained in examples 1-1 to 1-5 and comparative examples 1-1 to 1-3 to a glass plate using a spin coater, and then heating and curing the composition at 200 ℃ for 30 minutes. The thickness of the coating film after curing was 3 μm.
For the test pieces, gamma-butyrolactone (gamma-BL) and N-methylpyrrolidone (NMP) were added dropwise, respectively, and left for 10 minutes. Then, the substrate was washed with water, and was [. Circinata ] if the portion to which the solvent was added was not changed at all, and was [. Circinata ] if a trace of the solvent remained slightly, but was lost by wiping, and was ×. If a trace of the solvent remained was not lost by wiping, and was x if the entire surface was discolored.
(3) Solvent resistance test-2
A solvent resistance test of the cured product was carried out in the same manner as in the solvent resistance test-1 except that the curing temperature was set at 230 ℃ in the preparation of the test piece.
The photosensitive resin compositions of examples 1-1 to 1-5 were less likely to thicken even at 40 ℃ and had good storage stability. Moreover, even in the case where the curing temperature was 200 ℃, good solvent resistance was exhibited as in the case of 230 ℃. On the other hand, it is also understood that the photosensitive resin compositions of comparative examples 1-1 to 1-2 were poor in storage stability because they were gelled at 40 ℃. It is also understood that the photosensitive resin composition of comparative example 3 has good storage stability by using the monomer B2 (EDCPA), but if the curing temperature is lowered from 230 ℃ to 200 ℃, the solvent resistance is lowered because the curing is insufficient.
Next, the following evaluation tests were carried out using the photosensitive resin compositions obtained in examples 2-1 to 2-5 and comparative examples 2-1 to 2-3. The results are shown in Table 5.
(1) Storage stability test-2
The photosensitive resin compositions obtained in examples 2-1 to 2-5 and comparative examples 2-1 to 2-3 were stored in an oven at 40 ℃ for one week. The viscosity immediately after polymerization and the viscosity after storage at 40 ℃ for one week were measured. The viscosity increase rate was calculated according to the following calculation formula. The viscosity (unit: mPas) was measured using a viscometer (trade name "LVDV2T", manufactured by Brookfield corporation) at a rotation speed of 60 and a temperature of: measured at 23 ℃.
P: viscosity immediately after polymerization, Q: viscosity after storage at 40 ℃ for one week.
Viscosity increase rate = (Q/P) × 100} -100.
(2) Solvent resistance test-3
Test pieces were prepared by applying the photosensitive resin compositions obtained in examples 2-1 to 2-5 and comparative examples 2-1 to 2-3 to a glass plate using a spin coater, and then heating and curing the composition at 200 ℃ for 30 minutes. The thickness of the cured coating film was 2 μm.
For the test pieces, gamma-butyrolactone (gamma-BL) and N-methylpyrrolidone (NMP) were added dropwise, respectively, and left for 10 minutes. Then, the substrate was washed with water, and was [. Circinata ] if the portion to which the solvent was added was not changed at all, and was [. Circinata ] if a trace of the solvent remained slightly, but was lost by wiping, and was ×. If a trace of the solvent remained was not lost by wiping, and was x if the entire surface was discolored.
(3) Solvent resistance test-4
A solvent resistance test of the cured product was carried out in the same manner as in the solvent resistance test-3 except that the curing temperature was set at 230 ℃ in the preparation of the test piece.
The photosensitive resin compositions of examples 2-1 to 2-5 were less likely to thicken even at 40 ℃ and had good storage stability. Moreover, even in the case where the curing temperature was 200 ℃, the solvent resistance was good as in the case of 230 ℃. On the other hand, it is also understood that the photosensitive resin compositions of comparative examples 2-1 to 2-2 are thickened at 40 ℃ and have poor storage stability. Further, it is found that the photosensitive resin composition of comparative example 2-3 has good storage stability by using the monomer B2 (EDCPA), but the solvent resistance is lowered because the curing temperature is lowered from 230 ℃ to 200 ℃ because the curing is insufficient.
Figure BDA0003783774750000341
Figure BDA0003783774750000351
Figure BDA0003783774750000361
Figure BDA0003783774750000371
Figure BDA0003783774750000381
The following describes the components used in the production examples, examples and comparative examples.
A monomer B1: methacrylic acid 3-oxatricyclo [3.2.1.0 2,4 ]Octane-6-ylmethyl ester (see reference example 1)
GMA: glycidyl methacrylate (manufactured by Nichio oil Co., ltd.).
cyclomerM100: 3, 4-epoxycyclohexylmethyl methacrylate (manufactured by DAICEL, inc.).
A monomer B2: acrylic acid 3, 4-epoxy tricyclo [5.2.1.0 2,6 ]Decan-9-yl ester with acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]A mixture of decane-8-yl ester (trade name "E-DCPA", manufactured by DAICEL, ltd.).
ST: styrene (FUJIFILM, wako pure chemical industries, ltd.).
MMA: methyl methacrylate (FUJIFILM, wako pure chemical industries, ltd.).
CHMI: cyclohexylmaleimide (manufactured by Nippon catalyst Co., ltd.).
VP: n-vinylpyrrolidone (manufactured by Tokyo chemical industry Co., ltd.).
MMPGAC: propylene glycol monomethyl ether acetate (manufactured by DAICEL, inc.).
PR 254: c.i. pigment red 254 (manufactured by tokyo chemical industry co.).
DISPERBYK-2000: an amine value of 4mgKOH/g and a nonvolatile matter of 40% (manufactured by BYK Chemie Japan).
DHPA: dipentaerythritol hexaacrylate (trade name "KAYARAD DPHA"; manufactured by Nippon Chemicals Co., ltd.).
1-hydroxycyclohexyl phenyl ketone (FUJIFILM, manufactured by Wako pure chemical industries, ltd.).
As a summary of the above, the configuration of the present invention and its variations will be described below.
[1]
A photosensitive resin composition comprising:
an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
the alkali-soluble resin is a copolymer comprising a constituent unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a constituent unit (B) derived from a compound represented by the formula (1) (in the formula (1), R is 1 And R 2 Each of which is the same or different and represents a hydrogen atom or a carbon atomAlkyl groups having a sub-number of 1 to 7. X represents a single bond or a divalent hydrocarbon group optionally containing heteroatoms. Y represents a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer of 0 to 7), wherein the alkali-soluble resin is a copolymer having an exothermic peak top temperature of 180 to 220 ℃ which appears when the temperature is raised at a rate of 5 ℃/min using a differential scanning calorimeter.
[2]
The photosensitive resin composition according to [1], wherein,
the compound represented by the formula (1) is the formula (1 a) (wherein R is 1 、R 2 X, Y and n are the same as those described in the formula (1).
[3]
The photosensitive resin composition according to [1] or [2], wherein,
the copolymer further comprises a constituent unit (C) derived from at least one compound selected from the group consisting of the following (C1) to (C4),
(c1) Styrene optionally substituted with alkyl;
(c2) An N-substituted maleimide;
(c3) An N-vinyl compound; and
(c4) An unsaturated carboxylic acid derivative represented by the formula (2) (wherein R is 11 Represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 12 Represents a hydrocarbon group optionally containing heteroatoms. Z represents a heteroatom).
[4]
The photosensitive resin composition according to any one of [1] to [3],
the copolymer further contains a constituent unit derived from (meth) acrylamide or (meth) acrylonitrile as the constituent unit (D).
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein,
the proportion of the constituent unit (A) to the total constituent units of the copolymer is 2 to 60 wt%, 3 to 40 wt%, or 5to 20 wt%.
[6]
The photosensitive resin composition according to any one of [1] to [5], wherein,
the proportion of the constituent unit (B) to the total constituent units of the copolymer is 40 to 98 wt%, 60 to 95 wt%, or 75 to 90 wt%.
[7]
The photosensitive resin composition according to any one of [3], [5] and [6],
the proportion of the constituent unit (C) is 0 to 85 wt%, 1 to 60 wt%, 2 to 40 wt% relative to the total constituent units of the copolymer.
[8]
The photosensitive resin composition according to any one of [3] and [5] to [7],
the proportion of the constituent unit (A) to the total constituent units of the copolymer is 2 to 60 wt%, the content of the constituent unit (B) is 40 to 98 wt%, and the content of the constituent unit (C) is 0 to 85 wt%.
[9]
The photosensitive resin composition according to any one of [1] to [8],
when the copolymer contains the constituent unit (a) and the constituent unit (B) and does not contain the constituent unit (C), the total amount of the constituent unit (a) and the constituent unit (B) is 90 wt% or more, 95 wt% or more, 99 wt% or more, or substantially 100 wt% with respect to all the constituent units, and when the copolymer contains the constituent unit (a), the constituent unit (B), and the constituent unit (C), the total amount of the constituent units (a) to (C) is 90 wt% or more, 95 wt% or more, 99 wt% or more, or 100 wt% with respect to all the constituent units.
[10]
The photosensitive resin composition according to any one of [1] to [9],
the copolymer has a weight average molecular weight (Mw) of 1000 to 1000000, 3000 to 300000, or 5000 to 100000.
[11]
The photosensitive resin composition according to any one of [1] to [10],
the copolymer has a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: mw/Mn) of 5.0 or less, 1.0 to 4.5, or 1.0 to 4.0.
[12]
The photosensitive resin composition according to any one of [1] to [11],
the polymer has a peak temperature of 180 to 220 ℃ at an exothermic peak occurring when the polymer is heated at a rate of 5 ℃ per minute using a differential scanning calorimeter.
[13]
The photosensitive resin composition according to any one of [1] to [12],
also comprises color materials.
[14]
The photosensitive resin composition according to [13], wherein,
the color material is a pigment and/or a dye.
[15]
The photosensitive resin composition according to [13] or [14], wherein,
the content of the color material is 3 to 50 wt% and 5to 30 wt% relative to the solid content of the photosensitive resin composition.
[16]
The photosensitive resin composition according to any one of [1] to [15], wherein,
the photopolymerizable compound contains at least one selected from the group consisting of a polyfunctional vinyl compound, a polyfunctional thiol compound, and a polyfunctional epoxy compound.
[17]
The photosensitive resin composition according to any one of [1] to [16],
the content of the photopolymerizable compound is 10 to 300 parts by weight, 30 to 200 parts by weight, or 40 to 150 parts by weight based on 100 parts by weight of the alkali-soluble resin, and when the photosensitive resin composition contains the color material, the content of the photopolymerizable compound is 10 to 1000 parts by weight, 50 to 600 parts by weight, or 100 to 500 parts by weight based on 100 parts by weight of the color material.
[18]
A cured product of the photosensitive resin composition according to any one of [1] to [17 ].
[19]
A color filter which is a cured product of the photosensitive resin composition according to any one of [1] to [17 ].
[20]
A member for a display device or a display device, comprising the color filter according to [19 ].
Industrial applicability of the invention
The invention disclosed herein provides a photosensitive resin composition which has excellent storage stability, excellent curing reactivity, and excellent solvent resistance of a cured product. Also provided are a cured product of the photosensitive resin composition having the above properties, a color filter as the cured product, and a member for a display device or a display device provided with the color filter.

Claims (8)

1. A photosensitive resin composition comprising:
an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
the alkali-soluble resin is a copolymer comprising a constituent unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a constituent unit (B) derived from a compound represented by the following formula (1),
[ chemical formula 1]
Figure FDA0003783774740000011
In the formula, R 1 And R 2 Each represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms; x represents a single bond or a divalent hydrocarbon group optionally comprising heteroatoms; y represents a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom; n represents an integer of 0 to 7,
wherein the alkali-soluble resin is a copolymer having a peak temperature of an exothermic peak of 180 to 220 ℃ at a temperature rise of 5 ℃/min using a differential scanning calorimeter.
2. The photosensitive resin composition according to claim 1,
the copolymer further comprises a constituent unit (C) derived from at least one compound selected from the group consisting of the following (C1) to (C4),
(c1) Styrene optionally substituted with alkyl;
(c2) An N-substituted maleimide;
(c3) An N-vinyl compound; and
(c4) An unsaturated carboxylic acid derivative represented by the following formula (2),
[ chemical formula 2]
Figure FDA0003783774740000021
In the formula, R 11 Represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R 12 Represents a hydrocarbon group optionally containing a heteroatom, and Z represents a heteroatom.
3. The photosensitive resin composition according to claim 2,
the proportion of the constituent unit (A) is 2 to 60 wt%, the proportion of the constituent unit (B) is 40 to 98 wt%, and the proportion of the constituent unit (C) is 0 to 85 wt%, based on the total constituent units of the copolymer.
4. The photosensitive resin composition according to any one of claims 1 to 3,
also comprises color materials.
5. The photosensitive resin composition according to claim 4,
the color material is a pigment and/or a dye.
6. A cured product of the photosensitive resin composition according to any one of claims 1 to 5.
7. A color filter which is a cured product of the photosensitive resin composition according to any one of claims 1 to 5.
8. A member for a display device or a display device, comprising the color filter according to claim 7.
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